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Ca' Foscari University of Venice | UNIVE · Department of Environmental Sciences, Informatics and Statistics

This review reports on the competition/collaboration among intertwined base‐catalyzed acyl cleavage bimolecular mechanism (BAc2)/base‐catalyzed alkyl cleavage bimolecular mechanism (BAl2) or the related acid catalyzed mechanisms AAc2/AAl2 and AAl1 concerning Carbonates chemistry also in comparison with Esters reactivity. A consistent analysis of th...

Keggin-type heteropolyacids have been used as catalyst for the selective oxidation of olefins to the corresponding epoxides in multiphase conditions (isooctane/Aliquat 336/water). Multiphase system allowed achieving a higher conversion (72%) and selectivity (70%) to epoxide than the corresponding homogeneous or biphasic systems in the presence of t...

This review focuses on the use of dialkyl carbonates (DACs) as green reagents and solvents for the synthesis of several 5- and 6-membered heterocycles including: tetrahydrofuran and furan systems, pyrrolidines, indolines, isoindolines, 1,4-dioxanes, piperidines, and cyclic carbamates. Depending on the heterocycle investigated, the synthetic approac...

A sustainable methodology to synthesise and screen libraries of new low-environmental impact products, suitable for removing graffiti and murals from historic building, masonries and stone artworks has been developed. This approach provided a novel series of two-component systems by combining silica sol-gel chemistry and dimethyl carbonate. The sol...

These words were spoken by Irina Bokova, Director-General of UNESCO, in her address to the PhosAgro/UNESCO/IUPAC Award-Giving Ceremony in St Petersburg, 2 June 2017 [

The reactivity of β-aminocarbonates as anisotropic electrophiles has been investigated with several phenols. Products distribution shows that the regioselectivity of the anchimerically driven alkylation reaction depends on the nucleophiles. The results suggest that in the presence of nucleophiles that are also good leaving groups, the reaction take...

The worldwide urge to embrace a sustainable and bio-compatible chemistry has led industry and academia to the development of chlorine-free methodologies focused on the use of CO2 and CO2-based compounds...

Cyclization of 2-(2-hydroxyethyl)phenol via DMC chemistry in acidic conditions is herein discussed for the first time. Reaction conditions have been investigated and optimized. This substrate is quite appealing as it incorporates a 2-hydroxyethyl moiety in ortho to the aromatic hydroxyl group capable of stabilizing the related phenonium ion. When t...

Direct synthesis of dimethyl isosorbide (DMI) from D-sorbitol via dimethyl carbonate (DMC) chemistry is herein firstly reported. High yield of DMI was achieved using nitrogen superbase 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) as catalyst and performing the reaction in a stainless steel autoclave by increasing the temperature from 90°C to 200 °C. I...

In this review the reactivity of the bio-based platform compounds D-sorbitol and isosorbide with green reagents and solvent dimethyl carbonate (DMC) is reported. Dehydration of D-sorbitol via DMC in the presence of catalytic amounts of base is an efficient and viable process for the preparation of the industrially relevant anhydro sugar isosorbide....

Dialkyl carbonates (DACs) as reagents have found recent application in phosgene-free synthesis of both linear and cyclic carbamates. Different types of catalysts have been investigated for the carbamoylation of aniline via dimethyl carbonate (DMC) in batch. The possibility of conducting this reaction in a fixed-bed continuously fed reactor has been...

Different synthetic approaches to methylethers by reaction of alcohols with dimethyl carbonate (DMC) have been reported. Direct methylation has been achieved in good yields using basic alumina or hydrotalcite KW2000 as catalyst either in batch or continuous-flow conditions. A two-step synthetic approach, consisting of carboxymethylation of the pare...

The substitution of a chlorine atom with a carbonate moiety in mustard compounds has led to a new class of molecules, namely mustard carbonates that have retained the reactivity of the well-know toxic iprites, but are safe for the operator and the environment. In this paper, for the first time, the influence of the leaving group on the anchimeric e...

Review: synthesis of sulfur and nitrogen (half-)mustard carbonate analogs and their reactivity as novel, green electrophiles

The reactions of isosorbide and its epimers, isomannide and isoidide, with dimethyl carbonate have been herein investigated as easy access to bio-based products by a free-halogen chemistry approach. Isosorbide and its epimers show a different reactivity in bimolecular nucleophilic substitution with dimethyl carbonate (DMC). Carboxymethylation react...

A high yielding synthesis of 1,3-oxazinan-2-ones starting from 3-amino-1-propanols and ethylene carbonate (EC) in the presence of catalytic amount of triazabicyclodecene (TBD) is herein reported. The formation of six-membered cyclic carbonates was achieved by intermolecular cyclization reaction via double BAc2 mechanism. Cyclization reactions have...

Sulfur and nitrogen (half-)mustard carbonate analogues are a new class of compounds, easily synthesized by methoxycarbonylation reaction of the parent alcohols with dialkyl carbonates. In this work, their reactivity as novel, green electrophiles is reported. Reactions have been conducted in autoclave conditions at high temperature (180°C), under pr...

Catalytic amount of a nitrogen bicyclic base, i.e., DABCO, DBU and TBD is effective for the one-pot synthesis of heterocycles from 1,4-, 1,5-diols and 1,4-bifunctional compounds via dimethyl carbonate chemistry under neat conditions. Nitrogen bicyclic bases, that previously showed to enhance the reactivity of DMC in methoxycarbonylation reaction by...

Polycondensation of a nitrogen mustard carbonate analogue with aromatic diols under dilution conditions affords a series of azacrown ethers previously not easily accessible as they require multistep synthesis including protection, purification, cyclization and methylation. This novel synthesis relies upon the anchimeric effect of the nitrogen musta...

The reactions of isosorbide and its epimers, isomannide and isoidide, with dimethyl carbonate have been herein investigated as easy access to bio-based products by a free-halogen chemistry approach. Isosorbide and its epimers show a different reactivity in bimolecular nucleophilic substitution with dimethyl carbonate (DMC). Carboxymethylation react...

High yielding amination of ketones and benzaldehyde in acid-less conditions has been conducted on several ketones to achieve amides and nitriles. The reactivity of the selected substrates showed to depend on both oximation and Beckmann rearrangement reaction rates. Oximation allows the in-situ production of hydrochloric acid that enables Beckmann r...

Sulfur iprit carbonate analogues have been investigated in neat conditions at atmospheric pressure, in the presence and in the absence of a catalytic amount of base. Furthermore, their reaction mechanism has been discussed in detail. In these novel reaction conditions, sulfur mustard carbonate analogues, that previously showed poor or no reactivity...

This study describes the application of heteropolyacids H3PMo12O40, H4SiMo12O40, H4PMo11VO40, H5PMo10V2O40, H9PMo6V6O40, and a hybrid pyridine-modified heteropolyacid with Keggin structure for selective oxidation of alcohols to ketones or aldehydes using aqueous hydrogen peroxide and acetonitrile as solvent. Performance of these different catalysts...

High yielding one-pot oximation-Beckmann rearrangement of ketones to amides in ktrifluoroacetic acid has been conducted on several ketones and aldehydes. The substrate reactivity showed to depend on both oximation and Beckmann rearrangement reaction rate. In this synthetic procedure, trifluoroacetic acid acts as solvent, acid catalyst and organocat...

Alternative syntheses for the production of 3-benzyl-1,3-oxazinan-2-one are compared and evaluated employing green metrics. An environmental assessment has been performed using the algorithm recently developed by Andraos that takes into account the mass flows and the software EATOS that considers mass flows, environmental impacts of the substances...

A process of preparing cyclic ethers is described. The process involves the reaction of at least one organic compound such as a dioi or a polyol which it has at least one pair of hydroxyl groups separated by 4 or 5 carbon atoms, and which is capable of being converted into an ether linkage, with an organic carbonate in the presence of a base. The b...

Sulfur and nitrogen mustards are very toxic, yet versatile organic molecules with numerous applications. Herein, we report on a synthesis of a new class of green compounds, i.e., half-mustard and iprit carbonates, that result in new, unexplored, and safe molecules. Their chemical behavior with several nucleophiles and their reaction kinetics have b...

Over the last 20 years organic carbamates have found numerous applications in pesticides, fungicides, herbicides, dyes, pharmaceuticals, cosmetics, and as protecting groups and intermediates for polyurethane synthesis. Recently, in order to avoid phosgene-based synthesis of carbamates, many environmentally benign and alternative pathways have been...

A method for preparing dialkyl carbonates of dianhydrohexitol, includes the following steps: (a) preparing an initial reaction mixture containing at least one dianhydrohexitol, at least two mole equivalents of a dialkyl carbonate of formula and a transesterification catalyst; (b) heating the reaction mixture to a temperature greater than or equal t...

Polycyclic Aromatic Hydrocarbons are among the most persistent pollutants in various environmental matrices including soil. Because of their considerable toxicity even at low concentrations, it is essential to detect them at such very low levels (about ng/Kg) and to quantify them with precision and reliability. The objective of the present work is...

In the last twenty years DMC has been employed as an efficient methylating and methoxycarbonylating agent with several monodentate and bidentate nucleophiles, showing great selectivity and unexpected results. In this short review we report on yet another application of DMC chemistry i.e. the synthesis of 5-membered N- and O-heterocycles. In these r...

The reaction of 1,4-diols with dimethyl carbonate in the presence of a base led to selective and high-yielding syntheses of related five-membered cyclic ethers. This synthetic pathway has the potential for a wide range of applications. Distinctive cyclic ethers and industrially relevant compounds were synthesized in quantitative yield. The reaction...

A one-pot green synthesis of 1,3-oxazinan-2-ones from amines and 1,3-diols in the presence of a dialkyl carbonate and potassium tert-butoxide is described. Four dialkyl carbonates were utilised: dimethyl carbonate, diethyl carbonate, diprop-2-yl carbonate, and tert-butyl methyl carbonate. The more hindered the dialkyl carbonate used, the higher the...

Aliphatic and aromatic 1,4-bifunctional compounds bearing a primary alcoholic function and an amine can be efficiently cyclised with dimethyl carbonates in the presence of a base to achieve 5-membered N-heterocyclic compounds. This novel synthetic pathway is quantitative, one-pot and green as it does not involve the use of chlorinesolvents or reage...

Sulfur and nitrogen half-mustard compounds lose their aggressive properties when the chlorine atom is replaced by a carbonate moiety. The anchimeric effect of the novel mustard carbonate analogues is investigated. The reaction follows first-order kinetics, does not need any base, and occurs with –OH, –NH and acidic –CH nucleophiles. Most of these m...

Since the Industrial Revolution, chlorine has featured as an iconic molecule in process chemistry even though its production by electrolysis of sodium chloride is very energy-intensive. Owing to its high energy and reactivity, chlorine allows the manufacture of chlorinated derivatives in a very easy way: AlCl3, SnCl4, TiCl4, SiCl4, ZnCl2, PCl3, PCl...

A number of six-membered cyclic carbamates (oxazinanones) were synthesized from the reaction of a primary amine or hydrazine with a dicarbonate derivative of 1,3-diols in a one-pot reaction, in good yield, short time span, and in the absence of a solvent. The reaction proceeds in two steps: an intermolecular reaction to give a linear intermediate a...

In this work the synthesis of a tricyclic isosorbide derivative in moderate yield directly from the dicarboxymethyl isosorbide in a continuous-flow apparatus is reported. The tricyclic structure has been isolated as pure and fully characterized. This product confirms the potentiality of dimethylcarbonate (DMC) as dehydrating agent also for complica...

The Chemical Element: Chemistry's Contribution to Our Global Future CHEMISTRY FOR DEVELOPMENT Chemistry, Innovation and Impact Poverty and Disparities in Life Expectancy The Milennium Development Goals Science, Technology and Development Chemistry and Development Science and Technology for National Development Capacity Building: Some Key Requiremen...

H4PMo11VO40, H5PMo10V2O40 and H9PMo6V6O40 acids and an acidic pyridinium salt of H4PMo11VO40 were synthesized. They were characterized by FT-IR and the variations of their acid properties were determined by titration with n-butylamine. They proved to be highly active and selective catalysts for the hydrogen peroxide oxidation of methyl phenyl sulfi...

The synthesis of N-phenylcarbamate from aniline and dimethyl carbonate (DMC) in the presence of homogeneous, supported heterogeneous, and heterogeneous catalysts was investigated in batch conditions. First, a selection of homogeneous catalysts was studied and their reactivity in the same reaction conditions was compared to zinc acetate, a catalyst...

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

This experiment investigates the methylation of 2-naphthol with dimethyl carbonate. The volatility of the substrates, products, and co-products allows the reaction to be performed using a continuous-flow gas-phase setup at ambient pressure. The reaction uses catalytic quantities of base, achieves high conversion, produces little waste, and demonstr...

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

A model halogenated aryl ketone (4-chloropropiophenone 1) was subjected to mild catalytic hydrodehalogenation (p[H2] = 1 atm, T = 50 °C) in a multiphase system consisting of isooctane and an alkaline aqueous phase, in the presence of onium salts as phase-transfer agents. The chemoselectivity of the reaction was sharply influenced by the KOH concent...

The non-toxic compound dimethyl carbonate (DMC) can be used as a methylating and a methoxycarbonylating agent in place of methyl chloride and phosgene, respectively. We report here that DMC and other dialkyl carbonates (DAlkCs: dimethyl, diethyl and dibenzyl carbonates) allow very selective alkylations of a variety of CH2-acidic compounds. Both ary...

The non-toxic compound dimethyl carbonate (DMC) can be used as a methylating and a methoxycarbonylating agent in place of methyl chloride and phosgene, respectively. We report here that DMC and other dialkyl carbonates (DAlkCs: dimethyl, diethyl and dibenzyl carbonates) allow very selective alkylations of a variety of CH2-acidic compounds. Both ary...

This work describes the application of a multiphase system for the oxidation of alcohols to ketones or aldehydes, and the selective conversion of sulfides to sulfoxides or sulfones using Keggin-type heteropolyacids and hydrogen peroxide. Benzylic and secondary alcohols were oxidized to ketones or aldehydes at 70°C in good yield and selectivity. Sim...

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Published data on dimethyl carbonate as a safe reagent and solvent in organic synthesis are generalized and analyzed. The methods of dimethyl carbonate preparation and its use as methylating and carboxymethylating reagent are considered. The attention is focused on the environmentally safe processes corresponding to the green chemistry principles.

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

A number of carbamates were synthesised through a halogen-free process by reacting amines with symmetrical and unsymmetrical carbonates. The results obtained showed a specific trend of preferred leaving groups (in the dialkyl carbonates) depending on whether a catalyst or a base was used. On the other hand, investigations conducted on the preferred...

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

A green synthetic approach for dimethyl isosorbide (DMI) with dimethylcarbonate (DMC) in the presence of a base is reported. The easy methylation of isosorbide may be due to its unique structure (which enhances the nucleophilicity of the hydroxyl groups), and to the effect of the hydrogen bonding which increases the reactivity of the molecule towar...

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

A multiphase system consisting of a hydrocarbon solvent, a strong alkaline solution, and a quaternary onium salt, in the presence of a Pd/C catalyst with hydrogen at atmospheric pressure, allows the rapid and progressive displacement of the chlorine atoms from polyhalogenated benzenes. The onium salt in this case constitutes a third liquid phase in...

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

L'objet de ce travail de recherche est une contribution scientifique à la réussite de ce "Programme National" par une évaluation de la pollution agrochimique dans les sols répondant aux normes internationales, inexistantes dans notre pays. L'application des règles internationales environnementales est une mesure urgente à prendre en considération d...

The relationship between the catalytic activity and Pd particle size in Pd/ultradispersed diamond catalysts is established in the hydrodechlorination of 1,3,5-trichlorobenzene under multiphase conditions.

A series of dialkyl and methyl alkyl carbonates has been synthesized and their reactivity investigated. The behavior of preferential leaving and entering groups for the newly synthesized carbonates has been accurately investigated. Both experimental and computational studies agreed that the scale of leaving groups follows the trend: PhCH2O-, MeO- ≥...

The Lagoon of Venice has been receiving discharges of many classes of persistent organic pollutants (POPs) that have been accumulating in sediments and marine organisms and might represent an indirect threat to human health. In particular, the intensive harvesting of Manila Clam (Tapes philippinarum) and other traditional fishing activities carried...

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Following the preliminary studies on the reactivity of the ambident nucleophile phenylhydrazine with dimethyl carbonate, investigations involving para-substituted phenylhydrazines were carried out in order to probe differences in the reactivity within this class of nucleophile. Phenylhydrazines substituted by electron withdrawing or donating substi...

The decarboxylation reaction of dialkyl carbonates to give their related ethers was investigated. The reaction was carried out at atmospheric pressure and in the presence of hydrotalcite or basic alumina as catalysts without any solvent. The influence of several reaction parameters on the selectivity was studied (e.g. temperature, amount of catalys...

Phenols and naphthols were oxidized to the corresponding quinones using 60% p/V hydrogen peroxide and a substituted vanadium Keggin heteropolyacid (H4PMo11VO40.12H2O, HPA) as catalyst. The reactions were carried out at room temperature using acetone as solvent. This procedure was a mild and effective alternative for the phenol oxidation to quinones...

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

DMC is a versatile compound which represents an attractive ecofriendly alternative to both methyl halides (or dimethyl sulfate) and phosgene for methylation and carbonylation processes, respectively. DMC, produced nowadays by a clean process, possesses properties of no toxicity and biodegradability which makes it a true green reagent to be used in...

Polybrominated diphenyl ethers (PBDEs) are a class of widely used flame retardants that are incorporated into a wide range of consumer products such as household appliances, plastics, textiles and computers, to prevent fire. The main route of entry of these chemicals into the human body is via the food web, but occupational exposure may also occur...

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Keggin-type heteropolyacids have been used as catalyst for high-yielding oxidation reactions in multiphase conditions. This simple and efficient procedure promoted the conversion of anilines to the corresponding nitroso and nitro derivatives. In comparison with homogeneous system the oxidation from anilines to nitroso compounds and nitro compounds...

To explore the ambident electrophilic reactivity of dimethyl carbonate (DMC), reactions with the ambident nucleophile phenylhydrazine were investigated. When a Brönsted base was used, selective carboxymethylation occurred at N-1, after that several other compounds were produced selectively utilizing various conditions. Formation of these compounds...

Palladium P,C,P pincer complexes PdCl[{2,5-(R(2)PCH(2))(2)-C(5)H(2))Fe(C(5)H(5))] (1, R = iPr; 2, R = tBu) and {PdCl[(2,5-(tBu(2)PCH(2))(2)C(5)H(2)}Fe(C(5)H(5))]}OTf (3) catalyse Suzuki aryl coupling under homogeneous conditions as well as in multiphase system (triphase system: organic/Aliquat 336/aqueous solvent); the X-ray structure of complex 3,...

Green Chemistry is an inventive science based on fundamental research towards the development of new sustainable chemical processes. There is a great need to create a new type of chemistry focused on a new production system, in order to prepare the younger generation to get a greener future. The globalization pushes the chemistry community to adopt...

Various types of aromatic and aliphatic sulfides are selectively oxidized to sulfoxides and sulfones with good to excellent yields using H2O2 35% p/V in the presence of catalytic amounts of Keggin heteropolyacid (H5PMo11Al0.5V0.5O40) using acetonitrile as solvent.

The formation of diazonium salts from the corresponding primary aromatic amines and their reaction with potassium iodide to give the corresponding aryl iodide have been performed in a CO2/H2O solvent system. The weak acidity of this system (pH about 3) allowed the formation of triazenes as an intermediate via a reversible reaction.

The utilization and decomposition of chlorinated wastes without formation of di- oxins are challenges of great environmental importance. In this work, the catalytic reductive methods of chlorinated organics processing are described, focusing on catalyst development. Pd-containing catalysts are improved by modification of supports (use of ultra disp...